Bis-(1-{65 -aminopropyl-hydantoinyl-3)-alkanes

ABSTRACT

New bis-(1- gamma -aminopropyl-hydantoinyl-3)-alkanes, for example 1,6-bis-(1&#39;&#39;-( gamma -aminopropyl)-5&#39;&#39;,5&#39;&#39;dimethylhydantoinyl-3&#39;&#39;)-hexane or Beta , Beta &#39;&#39;-bis-(1-(3&#39;&#39;aminopropyl)-5,5-dimethyl-hydantoinyl-3)-diethyl ether, and their use as curing agents in curable moulding, coating and adhesive compositions which contain a polyepoxide compound, for example a liquid polyglycidyl ether of bisphenol A. Curing can be carried out at relatively low temperatures, for example at 40* C. The new type of curing agent bridges, in respect of its gradation of reactivity, a gap between aliphatic polyamines and cycloaliphatic polyamines. The new curing agents furthermore have the advantage relative to the aromatic polyamines of being non-toxic.

United States Patent Porret et al.

I 541 BlS-( l-y-AMINOPROPYL- HYDANTOINYL-3)-ALKANES [72] Inventors:Daniel Porret, Binningen; Juergen Habermeier, Allschwil, both ofSwitzerland [73] Assignee: Ciba-Geig y AG, Basel, Switzerland [22]Filed: Nov. 12, 1969 [2l] Appl. No.: 876,037

[30] Foreign Application Priority Data Nov. 22, 1968 Switzerland..l74l9/68 [52] US. Cl. ..260/309.5, 260/2 N, 260/47 EN,

[51] Int. Cl. ..C07d 49/32 [58] Field of Search ..260/309.5

[56] References Cited UNITED STATES PATENTS 3,296,208 l/l967 Rogers..260/309.5

FOREIGN PATENTS OR APPLICATIONS 572,090 3/1959 Canada ..260/309.51,546,270 10/1968 France ..260/309.S

OTHER PUBLICATIONS Chemical Abstracts Subject Index, A- I, Ju-

[451 Oct. 10,1972

ly-December, 1963 Vol. 59, page 1,1638 (I964). QDLASI Haga et al.(Abstract Japanese patent l7,232( 60)) Chem. Abst. Vol. 55, column17,655 (I961). QDLASI Sato l Chem. Abstr. Vol. 59, columns 3907- 8(I963). QDLASI Sato I] J. Chem. Soc. Japan, Pure Chem. Sec. Vol. 83,pages 318- 23(1962). QDl .C65j

Primary Examiner-Natalie Trousoe Attorney-Harry Goldsmith, Joseph G.Kolodny and Mario A. Monaco ABSTRACT New bis-(l-'y-aminopropyl-hydantoinyl-3)-alkanes, for example I ,6-bis-( l'-(7-aminopropyl )-5 ,5 '-dimethylhydantoinyl-Il' )-hexane or B,B'-bis-(l-( 3 aminopropyl)-5,5-dimethyl-hydantoinyl-3)-diethyl ether, and theiruse as curing agents in curable moulding, coating and adhesivecompositions which contain a polyepoxide compound, for example a liquidpolyglycidyl ether of bisphenol A. Curing can be carried out atrelatively low temperatures, for example at 40 C. The new type of curingagent bridges, in respect of its gradation of reactivity, a gap betweenaliphatic polyamines and cycloaliphatic polyamines. The new curingagents furthermore have the advantage relative to the aromaticpolyamines of being non-toxic.

5 Claims, No Drawings lt is known that epoxide resins can be cured bymonobasic or polybasic aliphatic, cycloaliphatic or aromatic amines.Curing with aliphatic amines, such as diethylenetriamine,triethylentetramine or hexamethylenediamine leads, even in the cold orat room temperature, to products having good mechanical properties whichhowever do not always suffice for the highest requirements. Thealiphatic polyamines are furthermore not physiologically harmless. Thecycloaliphatic polyamines, such as diaminodicyclohexylmethane, are as arule less toxic than the aliphatic polyamines but on the other hand curemore slowly, and at only moderately elevated cure temperatures (forexample 40 C.) it is in general not possible to achieve optimumproperties of castings or coatings. Curable mixtures of epoxide resinsand aromatic polyamines, such as phenylenediamine or4,4'-diaminodiphenylmethane, can as a rule only be cured at highertemperatures to give industrially usable products. Furthermore thearomatic amines are more or less strongly toxic.

Thus the following sequence of reactivity applies to the main classes ofamine curing agents known as curing agents for epoxide resins: aliphaticamines cycloaliphatic amines aromatic amines.

For practical requirements, a gap hitherto existed in the reactivitygradation between the aliphatic amines and the cycloaliphatic amines. ithas now been found that by the use of certain di-primary diaminescontaining two heterocyclic nuclei, namely bis-(l-y-aminopropylhydanloins), which have hitherto not been described inthe literature, it is possible to bridge this previous gap.

At only moderately elevated curing temperatures of 30 to 60 C. thesebis(y-aminopropylhydantoins) under comparable conditions yield mouldingsof improved mechanical properties, above all of better impact strengthand elongation at break, than the aliphatic and cycloaliphaticpolyarnines which are.

known as curing agents, The physiologically harmless newbis(y-aminopropylhydantoins) are furthermore. for many applications, afully equivalent replacement for the toxic aromatic amines hithertousual as curing agents for these purposes Admittedly some types of aminecuring agents for epoxidc resins have already been proposed in theliterature, in which one or more aminoalkyl groups are located on ahetcrocylic nucleus. Thus British Pat. Specification No. 869,484describes mono-aminoalkylpipcrazincs, such as aminoethylpiperazine, ascuring agents for cpoxide resins. This class of curing agents yieldsmouldings having good mechanical properties only at higher curingtemperatures, whereas brittle, industrially unusable castings areobtained at curing tempcralurcs Ulr'lllOUl 40 C.

French Pal. Specification No. l,399,l7land Austri an Pat SpecificationNo. 250,024 further describe Isin-tutrah dropyrirnidinc derivatives,which carry 8 ll m wherein the symbols R, R,, R,', R, and R, have thesame significance as in the abovementioned Formula (I), in a mannerwhich is in itself known. The hydrogenation is preferably carried out inthe presence of ammonia and a hydrogenation catalyst such as Raneynickel or Raney cobalt.

The bis-(B-cyanoethylhydantoins) of Formula (II) used as startingsubstances in the process according to the invention are industriallyconveniently accessible through the addition of acrylonitrile("cyanoethylation") in the presence ofa catalyst such as for exampleNaOH or KOH, to a bishydantoin of formula i ii wherein R, R,, R,', R,and R, have the same significance as in Formula (I). As bis(hydantoins)of For mula (Ill) there may for example be mentioned:bis(5,S-dimethylhydantoinylJ) methane, l,4-bis(5',5'

(Ill) dimethylhydantoinyl-3' l-butane, l,2-bis( 5 ,5dimethylhydantoinyl-3' )-ethane, LIZ-bist 5 ,5 dimethylhydantoinyl-3')-dodecane, l,6 bis( 5',5 dimethylhydantoinyl-3' l-hexane, [3 8'-bis(5',5 dimethylhydantoinyl-3l-diethyl ether. l,4-bisl5'-npropylhydantoinyl-Zt' )butane, l ,4-bis( 5 isopropvlhy (IV a and IV bcan be identical or different hydantoins) with 1 mol ofa dihalide offormula Hal R Hal v wherein Hal represents a halogen atom and R has thesame significance as in Formula (I), in the presence of 2 equivalents ofalkali. Hydantoins represented by formulas (IV a) and (IV b) can bereadily prepared from reference.

As hydantoins of formulas (iv a) or (IV 1)) there may for example bementioned: hydantoin, S-methyl-hydantoin, S-ethylhydantoin,S-propyl-hydantoin, l,3-diazaspiro(4.4)nonane-2,4-dione,1,3-diazaspiro(4.5)decane-2,4-dione, 5,5-diethyl-hydantoin, 5-methyl-5-ethyl-hydantoin and especially 5,5-dimethylhydantoin.

As dihalides of Formula (V) there may be mentioned: methylene chloride,l,2-dichlorethane, l,2- or l,3-dichloropropane, l,2- or [,3- or [,4-dichlorobutane, l,2- or l,3- or l,4- or 1,5 2,4-dichloropentane, thecorresponding dichlorohexanes, -heptanes, -octanes, -nonanes, -decanes,-undecanes, -dodecanes, -hexadecanes, -octadecanes, l,4-dichloro-2-butene, di-(2-chlorethyl) formal, di-(Z- chlorethyl)-ether,l,4-dichloro-2-methylbutane, l,3- dichloro-Z-hydroxy-propane,l,5-dichloro-2,2- dimethylpentane, di-(B-chlor-ethyl)-thioether,di-(fichloro-ethyl)-ether, l,2-, l,3- or l,4-dichlorocyclohexane,4,4'-dichlorodicyclohexylmethane, 4,4-dichlorodicyclohexyldimethylrnethane, l,2-, l,3- orl,4-dichloromethylbenzene, l,4-diiodobutane, l,5- dibromopentane,l,4-dibromo-2-butene, l,8-

dihromoctane, a,a'-dlbr0m0-0-, mor p-xylene, glycolbis-chloracetate andthe bis-monochloracetates of lower polyglycols.

Preferably, the w, w'-bis-(5,5-dimethyl-hydantoinyl- 3) derivatives ofstraight-chain hydrocarbons of the paraffin series are used as startingsubstances. The catalytic hydrogenation of thebis-(B-cyanoethyl-hydantoins) of Formula (ll) appropriately takes placein the presence of a hydrogenation catalyst and of ammonia. The presenceof ammonia largely suppresses the production of undesired by-products,such as secondary amines, condensed products and the like. Ammonia canfor example be employed in the gaseous or liquid form or in the form ofa solution in methanol, dioxan and other solvents. Raney nickel andRaney cobalt are particularly effective as hydrogenation catalysts. Itis also possible to use a cobalt oxide catalyst on a suitable carriermaterial, this catalyst being reduced to cobalt metal catalyst in thestream of hydrogen.

be carried out at atmospheric pressure and room temperature, butelevated pressures of 50 atmospheres and above, as well as elevatedreaction temperatures in the separated off, for example by filtration,and monia and solvent are distilled off.

As mentioned initially, the new diamines of Formula I) representvaluable curing agents for epoxide resins.

The subject of the present invention are hence also curable mixtureswhich are suitable for the manufacture of mouldings, impregnations,coatings and adhe sive bonds, and which are characterized in that theycontain (a) a polyepoxide compound with an average of more than oneepoxide group in the molecule; and (b) as the curing agent, a di-primarydiamine containing two hydantoin rings, of Formula (I).

Appropriately, 0.5 to 1.3 equivalents, preferably about l.0 equivalent,of nitrogen-bonded active hydrogen atoms of thebis(y-aminopropylhydantoin) of Formula (I) are used per 1 equivalent ofepoxide groups of the polyepoxide compound (a).

Possible polyepoxide compounds (a) are above all those with an averageof more than one glycidyl group, B-methylglycidyl group or2,3-epoxycyclopentyl group bonded to a hetero-atom (for example sulphur,preferably oxygen or nitrogen); the following may be aliphatic alcohols,such as l,4-butanediol, or polyal glycols, such as polypropyleneglycols; diglycidyl ethers or polyglycidyl ethers cycloaliphaticpolyols, such as 2,2-bis-(4-hydroxycyclohexyl)propane; diglycidyl ethersor polyglycidyl ethers of polyhydric phenols, such as resorcinol,bis-(phydroxyphenyl)methane, 2,2-bis(p-hydroxyphenyl)- propanediomethane), 2,2-bis(4'-hydroxy 3,5- dibromophenyl)-propane, l, l,2,2-tetrakis-(p-hydroxyphenyl)ethane, or of condensation products ofpolyglycidyl esters of polybasic carboxylic acids, such terephthalicN,N,N ,N -tetraglycidyltriglycidyl-isocyanurate;

N,N-diglycidyl-toluidine, bis(p-aminophenyl)-methane;N,N-diglycidyl-ethyleneurea; N,N'-diglycidyl-5,5- dimethyl-hydantoin,N,N'-diglycidyl-5-isopropyl-hydantoin;N,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6- dihydro-uracil.

If desired, active diluents such as for example styrene oxide, butylglycidyl ether, isooctyl glycidyl ether, phenylglycidyl ether, cresylglycidyl ether or glycidyl esters of synthetic highly branched mainlytertiary lower temperature (for example about 40 C.) and the post-curingat a higher temperature (for example 100 C.).

The curing can, if desired, also be carried out in two stages by firstprematurely stopping the curing reaction or carrying out the first stageat room temperature or at only slightly elevated temperature, whereupona curable precondensate which is still fusible and soluble (a so-calledB-stage) is obtained from the epoxide component (a) and the amine curingagent (b). Such a precondensate can for example serve for themanufacture of prepregs," compression moulding compositions orespecially sintering powders.

In order to shorten the gelling times or cure times, known acceleratorsfor curing with amines, for example monophenols or polyphenols, such asphenol or diomethane, salicylic acid, tertiary amines or salts ofthiocyanic acid, such as Nl-LSCN, can be added.

The term curing" as used here denotes the conversion of the soluble,either liquid or fusible, polyepoxides into solid, insoluble andinfusible, three-dimensional crosslinked products or materials, and inparticular as a rule with simultaneous shaping to give mouldings, suchas castings, pressings, laminates and the like or two-dimensionalstructures such as coatings, lacquer films or adhesive bonds.

The curable mixtures according to the invention from polyepoxidecompounds (a) and bis('y-aminopropylhydantoins) of Formula (I) as curingagents can furthermore be mixed, in any stage before curing, with usualmodifiers such as extenders, fillers and reinforcing agents, pigments,dyestuffs, organic solvents, plasticizers, flow control agents, agentsfor conferring thixotropy, flameproofing substances or mould releaseagents.

As extenders, reinforcing agents, fillers and pigments which can beemployed in the curable mixtures accordalcohol, ethylene glycolmonomethyl ether, monoethyl ether and monobutyl ether.

Dibutyl, dioctyl and dinonyl phthalate, tricresyl phosphate, trixylenylphosphate and also polypropylene glycols can be employed as plasticizersfor modifying the curable mixtures.

Silicones, cellulose acetobutyrate, polyvinyl butyral, waxes, stearatesand the like (which in part are also employed as mould release agents)can be added as flow control agents when employing the curable mixtures,especially in surface protection.

Especially for use in the lacquer field, the polyepoxide compounds canfurthermore be partially esterified in a known manner with carboxylicacids, such as, especially, higher unsaturated fatty acids. It isfurthermore possible to add other curable synthetic resins, for examplephenoplasts or aminoplasts to such lacquer resin formulation.

The curable epoxide resin mixtures according to the invention are aboveall employed in the fields of surface protection, the electricalindustry, laminating processes and the building industry. They can beused, in a formulation suited in each case to the special end use, inthe unfilled or filled state, optionally in the form of solutions oremulsions, as paints, lacquers, as sintering powders, compressionmoulding compositions, injection moulding formulations, dipping resins,casting resins, impregnating resins, binders and adhesives, as toolresins, laminating resins, sealing and filling compositions, floorcovering compositions and binders for mineral aggregates.

in the examples which follow, unless otherwise stated, parts denoteparts by weight and percentages denote percentages by weight. Parts byvolume and parts by weight bear the relation of the milliliter to thegram.

The following epoxide resins were used for the manufacture of curablemixtures described in the examples:

EPOXlDE RESIN A Polyglycidyl ether resin (commercial product)manufactured by condensation of diomethane (2,2-bis(p-hydroxyphenyl)-propane) with a stoichiometric excess ofepichlorhydrin in the presence of alkali, consisting mainly ofdiomethane-diglycidyl ether of formula which is liquid at roomtemperature and has the following characteristics: Epoxide content: 5.15.5 epoxide equivalents/kg Viscosity (Hoeppler) at 25 C.: 9,000 13,000cP EPOXIDE RESIN B Liquid hexahydrophthalic acid diglycidyl ester(commercial product) Epoxide content: 6.3 epoxide equivalents/kgViscosity (Hoeppler) at 25C.: 475 cP EPOXlDE RESIN C Polyglycidyl etherresin (commercial product) consisting mainly of the diglycidyl ether of2,2-bis-(4'- hydroxycyclo-hexyl)-propane of formula CHI which is liquidat room temperature and has the fol s lowing characteristics: Epoxidecontent: 4.46 epoxide equivalents/kp Viscosity (Hoeppler) at 25 C.: 2140cP For determination of the mechanical and electrical properties of thecurable mixtures described in the examples which follow, sheets of 135 X135 X 4 mm were manufactured for determining the flexural strength,deflection, impact strength and water absorption. The test specimens (6010 4 mm) for determining the water absorption and for the flexing testand impact the arcing resistance and the tracking resistance (VDE 0303).

MANUFACTURING EXAMPLES EXAMPLE 1 a. A solution of 588 g ofl,6-bis-(5',5'-dimethylhydantoinyl-3')-n-hexane in 600 ml of dioxane ismixed at 1 C. with 2 ml of 30 percent strength aqueous sodium hydroxidesolution, whilst stirring. 194 g of acrylonitrile (3.65 mols) are addeddropwise over the course of minutes and the heating bath is removed. Thetemperature of the reaction mixture remains at 108 C. and the pH isabout 8. During the dropwise addition the aerylonitrile boils underreflux, and at the end of the dropwise addition practically all theaerylonitrile has reacted. The mixture is stirred for a further 20minutes at 109 C. and 1 liter of water is then added. A clear solutionresults, from which colorless crystals precipitate on slow cooling to 10C. These are filtered off, rinsed with a little water and dried in vacuoat 60 C. 679 g (87.9 percent of theory) of l,6-bis-( 1 '(B-cyanethyl)-5',5'- dimethyl-hydantoinyl-3')-n-hexane of melting point 109 to 1 14C. are obtained. The material is recrystallized from 600 g of methanoland 612 g of pure product of melting point 1 l2.5-113.8 C. are obtained.

Elementary analysis shows:

b. 44.5 g of l ,6-bis-[ I'-(B-cyanethy1)-5,5'-dimethylhydantoinyl-3]-n-hexane (0.1 mol) are mixedwith 500 g of methanol, 50 g of ammonia gas and 5 g of Raney nickel andhydrogenated in 22 hours at 24 C. in a duck-shaped shaking vessel, undernormal pressure. The resulting solution is filtered to remove the nickeland is subsequently concentrated on a rotary evaporator until constantweight is reached C./0.l mm Hg). 45.2 g (100 percent of theory) of1,6-bis-[1'-('y-aminopropyl)-5 ',5 '-dimethylhydantoinyl-3' ]-n-hexaneof formula O=C'-NCHICH2CHR NHQ CH: N-(CHzh-N f \E/ are obtained in theform of greenish crystals. The product has the followingcharacteristics: Melting point: 65 to 67 C. Amine group content: 4.06equivalents/kg (corresponding to 91.8 percent of theory). EXAMPLE 2 a. Amixture of 269.93 g of B,B'-di-(5,5-dimethylhydantoinyl -3)-diethylether (0.828 mol) and 89.04 g of acrylonitrile (1.68 mols) is heated to50 C. and 1.2 ml of 30 percent strength aqueous sodium hydroxidesolution are then added. The pasty reaction mixture is heated to 55 C.whilst stirring, whereupon a strongly exothermic reaction begins; afterremoval of the heating bath, the temperature of the mixture furtherrises to 1 12 C. After about 15 minutes the reaction has ended; themixture is stirred for a further 30 minutes at C. and the excessaerylonitrile is distilled off under a gradually increasing vacuum (62mm Hg to 15 mm Hg). 3.6 g of acrylonitrile are thus recovered (theory4.2 g).

354.3 g (99.1 percent yield) of fl,B'-bis-[ l-(2'-cyanethyl)-5.5-dimethylhydantoinyl-3]-diethyl ether are obtained as avery viscous resin which is dark brown in color.

b. A mixture of 515 g of B,B'-bis-[ l-(2'-cyanethyl)- 5,5-dimethylhydantoinyl-3l-diethyl ether (1.19 mols), 660 ml of dioxane, 35g of Raney nickel and 260 g of ammonia gas is hydrogenated in 6 hours atC. under 100 atmospheres hydrogen pressure. The reaction mixture isworked-up in accordance with Example 1b) and 491.5 g (cor responding to93.4 percent of theory) of B,B'-bis- [1-(3'-aminopropyl)-5,S-dimethyl-hydantoinyl-3 ]-diethyl ether of formulaNCHzCH:-0-CH:CH:N\ of, c E on.

Found Calculated 5 are obtained in the form of a yellowish viscous oil.The

product has the following characteristics: Viscosity (Hoeppler) at 25C.: 29,300 cP 59.23%c 59.44%(3 7.18 as 11 7.26 11 Amine group content:4.31 equ1va1ents/kg(= 95.6 per- 19.09%N 18.91%N

cent of theory EXAMPLE 3 9 a. 201 g (0.75 mol) ofbis-(5,5-dimethylhydantoinyl- 3)-methane are suspended in 240 ml ofdimethylformamide in a stirred flask equipped with a reflux condenser,internal thermometer and dropping funnel, whilst stirring. After adding0.6 ml of N 5 NaOH the suspension is first warmed to about 120 C.,internal temperature at a constant bath temperature of 142 C., afterwhich the dropwise addition of a total of 84 g of acrylonitrile 1.6mols) is started. During the dropwise addition the internal temperaturerises to about 152 C. The reaction is allowed to continue for about afurther hour, in the course of which the internal temperature drops toabout 135 C. The solvent is now completely removed on a rotaryevaporator, initially under a waterpump vacuum and at a bath temperatureof 140 C. and subsequently at about 0.1 mm Hg. After cooling, 283 g (101percent of theory) of colorless crystals are obtained. For purificationthis crude product was recrystallized from 1,400 ml of methanol. Themelting point of the bis-[ l {,6-cyanoethyl)-5,5-dimethylhydantoinyl-3l-methane is 139.4- 141.2C.Elementary analysis shows:

b. 194 g (0.52 mol) of the recrystallized bis-[ l-(B- cyanoethyl)-5,5-dimethylhydantoinyl-3 l-methane described above are suspended in 250ml of isopropyl alcohol and hydrogenated, after addition of 20 g ofRaney nickel, in a stirred autoclave in the presence of 60 g of ammoniagas, at a hydrogen pressure of 125 atmospheres at 100 C., over thecourse of about 6 hours.

The solution freed of catalysts by filtration is first completelyconcentrated on a rotary evaporator at about 80 C. bath temperature andabout 20 mm Hg. Remnants of volatile constituents which are stillpresent are removed at the same bath temperature but at about 0.1 mm Hg.

191.5 g (96.4 percent of theory) of abis-[l-(yaminopropyl)-5,5-dimethylhydantoinyl-3]-methane of formula 0product contains 4.95 NH, equivalents/kg (94.7 percent of theory).EXAMPLE 4 a. 84.4 g (0.2 mol) of 1,12-bis-(5'-dimethylhydantoinyl-3')-n-dodecane, dissolved in 50 ml ofdimethylformanide, 0.2 ml of 10 N NaOH and 22.2 g (0.42 mol) ofacrylonitrlle are reacted in accordance with the procedure described inExample (3a) and thereafter the reaction product is completely freed ofdimethylformamide. 102 g (96.7 percent of theory) of a dark brownviscous liquid are obtained. For further purification, the product isdissolved in 100 ml of methyl ethyl ketone, filtered hot after additionof active charcoal, and freed of the solvent.

b. 86 g of the purified crude product of 1,l2-bis-[1- (B-cyanoethyD-S ,5'-dimethylhydantoinyl-3 ]-ndodecane, obtained according to Example 4a),are dissolved in 100 ml of isopropyl alcohol and hydrogenated over thecourse of about 6 hours in accordance with the procedure described inExample (3b), in the presence of 9 g of Raney nickel and 45 g of ammoniagas; the mixture is then filtered and freed of volatile constituents.Since the product is evidently inadequately hydrogenated according tothe potentiometric titration, it is again hydrogenated under the sameconditions.

After working-up according to Example (3b) 78 g of l ,1 2-bis- 1'-(-y-aminopropyl)-5 ',5'-dimethylhydantoinyl-3 l-n-dodecane of formulaare obtained. According tion it contains 3.48 NH, equivalents/kg (93.5percent of theory). EXAMPLE 5 a. In accordance with the proceduredescribed in Example (3a), 84.6 g (0.25 mol) of l,4-bis-(5'-isopropylhydantoinyl-3')-n-butane are dissolved in 110 ml ofdimethylfonnamide and reacted with 28.1 g (0.53 mol) of acrylonitrile inthe presence of 0.2m] of 10 N NaOH Following the post-reaction, 0.2 g ofactive charcoal are added to the reaction mixture; it is then filteredand the dimethylformamide is completely removed under reduced pressure.110 g of a dark brown viscous liquid are obtained, corresponding to ayield of 100 of theory. b. 102 g ofl,4-bis-[l-(B-cyanoethyl)-5'-isopropyl- CH; CH

which is blue in color because of its slight nickel-amine complexcontent. According to the potentiometric titration of the aqueoussolution with 1 N HCl, the

hydantoinyl-3'-]-n-butane are dissolved in ml of isopropyl alcohol andhydrogenated in accordance with the procedure indicated in Example tothe potentiometric titra- 12 EXAMPLE u I g of epoxide resin A arehomogeneously mixed at 40 C. with 55.5 g of B,B'-bis-[l-(3'-aminopropyl)- 5,S-dimethyl-hydantoinyl-3 ]-diethyl ether and theresulting mixture (sample C) is cast into aluminum moulds (135 X I35 X 4mm) warmed to 40 C. Curing takes place for 24 hours at 40 C. Theproperties of the castings can be seen from Table II below:

are obtained in the form of a brown highly viscous oil which accordingto the potentiometric titration contains 4 NH equivalents/kg (90 percentof theory).

USE EXAMPLES EXAMPLEI l00 g of epoxide resin A (liquiddiomethanediglycidyl ether having an epoxide content of 5.25 epoxideequivalents/kg and a viscosity at 25 C. of about 9,500 c?) arehomogeneously mixed at 40 C. with 59 g ofl,6-bis-[1'(y-aminopropyl)-5',5'- dimethylhydantoinyl-3'l-n-hexaneaccording to Example 1, having an amine group content of 4.06equivalents/kg (corresponding to a ratio of equivalents of epoxidegroups to equivalents of nitrogen-bonded active hydrogen atoms approx.1:1 and the resulting mixture (sample A) is poured into aluminum moulds(135 X 135 X 4 mm) prewarmed to 40 C. and subjected to the followingcuring cycle: 24 hours, 40 C. +6 hours, l00" C.

For comparison, a known curable mixture is manufactured from 100 g ofepoxide resin A and 29 g of 2- methyl-3,3-bis-(y-aminopropyl)-3,4,5,6-tetrahydropyrimidine (sample B). This comparison mixture is curedanalogously to the sample A, according to the invention, for 24 hours at40 C. and then for 6 hours at 100 C.

Table 1 below quotes the properties of castings obtained with the sampleA according to the invention and the known sample B:

This experiment shows that the test specimens from sample A according tothe invention possess a higher impact strength and deflection than thetest specimens obtained under analogous curing conditions from the knownsample B.

TABLE [I Sample C g of Amine Curing Agent per I00 3 of Epoxide Resin A55.5

Flexural strength (VSM 77,l03) l2.2 kg/mm Deflection (VSM 77,103) [7.8mm Impact strength (VSM 77,105) l6.8 cmkglm Heat distortion pointaccording to Martens (DIN 53,458) 59C Water absorption 4 days, ZOC 0.39%

COMPARISON EXPERIMENT For comparison, samples D, E, F and G wereprepared, in each case mixing g of the liquid epoxide resin A used inexample [I (bisphenol-A- polyglycidyl ether resin with an epoxidecontent of 5.35 epoxide equivalents/kg) with the equivalent amountsgiven below in Table Ill of triethylenetetramine (sample D),l,6-hexamethylenediamine (sample E), bis-(4amino-B-methyI-cyclohexyl)-methane (sample F) andl-(2'-aminoethyl)-piperazine (sample G) at 40 C. The mixtures were curedfor 24 hours at 40 C. analogously to sample C according to example II,and the properties of the castings were determined.

The results can be seen from Table Ill below:

TABLE III Sample D1 E F5 o G. 01 amino curing ant 10 16 33 23.

per 1(1) g. of epoxl e resin A.

Flexural strength VSM Heat distortion int aceordirg to ns DIN Waterabsorption 4 days, 0. 21 0. 29

20 0. (percent).

1 'Irlethylene-tetramlne.

2 HemrnethyIene-dlamlne.

l Bls-( l-amino-3-methyleyqlohexyl) methane.

Brittle, not

Brittle, not maehinable.

machlnable.

100 g of epoxide resin at a time were homogeneously mixed at 40 C. with51.3 g of bis-[ l-(y-aminopropyU- 5,5-dimethylhydantoinyl-3 ]-methaneand with 73.5 g of 1,] 2-bis-[ l'-(-y-aminopropyl)-5',5'dimethylhydantoinyl-3'i-n-dodecane respectivelyand the resulting mixtures were poured into prewarmed alumininium moulds1 35 X I35 X 4 mm) analogously to Example I.

The mixtures were in each case cured for 24 hours at 40 C. andpost-cured for 6 hours at 100 C. Test specimens of dimensions 60 X 10 X4 mm for determining the flexural strength, deflection, impact strengthfor 6 hours at 100 C. The test specimens were then cooled to roomtemperature and the tensile shear strength of the adhesive bond wasdetermined in the tensile test. A tensile shear strength of 0.89 kg/mmwas obtained as the mean value from three determinations.

EXAMPLE V Three different bis-[ 1 -('y-aminopropyl)-hydantoinyl- 3l-alkanes were used as curing agents for epoxide resin B (liquidhexahydrophthalic acid diglycidyl ester with an epoxide content of 6.3epoxide equivalents/kg and a viscosity at 25 C. of 475 cP).

The diamines indicated in the table below were in 15 each case carefullymixed with epoxide resin B in the and water absorption were manufacturedfrom the mixing ratio indicated A pal-t f the mixture was sheets of thecured shaped material thus obtained. ad on the ends, previouslyroughened by grinding The Properties of these test Specimens can be andcleaned by washing with acetone, of test strips of from Table Iv below.an aluminum alloy (registered trade name Anticorodal B) of dimensionsI70 X X 1.5 mm. Two of these test strips at a time were so lined up bymeans of a gauge TABLE IV that the ends spread with the resin-curingagent mixture overlap by ID mm, and were then fixed in this posi-Diamine Bisll-(y-aminopro- 1,l2-b[s-[l-$ -aminoby means of a hose P-resln'cul'lng age!L y )-6, m y p prU- 25 mixture here used as theadhesive was cured for 24 mi iii ii i oifiig ifii hours at 40 C. andpost-cured for 6 hours at 100 C. dwwam The test specimens were thencooled to room temperaa i u na e -3 3- ture and the shear strength ofthe adhesive bond was girlmg'ofepmde mm determined in the tensile test(mean value of three Curing conditions 24 hours at 40 0. plus 6 hours at100 C. tests) Flexural strength (VSM 14.5 kgJmmfi. 9.6 kgJmmfl. g g vgz(VSM 77 103) n 0 mm 15 mm The remainder of the resin-curing agentmixture was Impact strength (vsM 42:9cm.lig:ier ri. 51.9 cmk gJcmJ.spread on aluminum sheets f dimensions 50 X 0 X 0.8 mm and the thinlayer coating thus obtained was ggfg g s i M1 percent 0 M2 percent. alsocured for 24 hours at 40 C. 6 hours at 100 C. After curing the coatingwas tested for scratch resistance, tackiness after wiping over with anacetonesoaked cottonwool pad and resistance towards bending EXAMPLE IVof the substrate.

10 g of epoxide resin A were carefully mixed with 6.4 The results of theindividual tests are summarized in g of l,4-bis-[l-('y-aminopropyl)-5'-isopropyl-hydan- Table V below:

TABLE v Diamine Bis-[th-aminopropyD-ib-dimethyl- M-bis-[V-(T-Brninopro1)-5- 1.12-bls[1'-( -amlnopropy)-5',5-d1methhydantoinyl-al-methane.lsopropylhydantoiny ]-nylhydantoinyMq-n-dodecane. U. of amine curingagent per 6.2 721R??? 8.9.

10 g. of epoxide resin B. Curing condittons.. 24 hours at 40 0. plus 6hours st100 C. Tensile shear strength on 1.01 kgJmm. 0.64 kgJmm. 1.11kgJmmfl.

Anticorodal B." Assessment of the cured coating.

Scratch-resistant coating which after Scratch-resistant but somewhatbrit- Scratch-resistant coating which after treatment with anacetonesoaked tlecoatingNolongerbec-nmes tacky treatment with anacetone-soaked cottonwool pad no longer becomes alter treatment with anecetonecottonwool pad no longer becomes tacky. withstands repeatedbending eottonwool pad.

of the metal sheet without tearing or flaking ofl.

toinyl-3]-n-butane and spread on the ends, previously roughened bygrinding and degreased by washing with acetone, of test strips of analuminum alloy (registered trade name Anticorodal B) of dimensions 170 X25 X 1.5 mm. Two of these test strips at a time were so lined up bymeans of a gauge that the ends spread with the resin-curing agentmixture overlap by 10 mm, and were then fixed in this position by meansof a hose clip.

The resin-curing agent mixture here used as the adhesive was cured for24 hours at 40 tacky and also withstands relpeated biending 01 the sheetmeta subs rate.

EXAMPLE Vl Curable mixtures with three different bis-[l-(yaminopropyl)-hydantoinyl-3-alkanes were manufactured as in exampleV, but with the difference that instead of epoxide resin B, epoxideresin C (liquid C. and post-cured and the resulting tensile shearstrength values of the lObOlll 022$ test specimens (mean of threedeterminations) and the 2. l,4-Bis-[l'-(-y-aminopropyl)-5-isopropylhydanassessment of the coating (curing asa thin layer) are toinyl-3l-n-butane. summarized in Table V] below. 3.1,6 Bisl '-(-y-aminopropyl)-5,5'-dimethylhydan- TABLE VI Diamine v rBis-llh-amino rop 1)-5,5-dimethl- 1,4-bis,[i(1-eminoprop l)-'-l,12-bis-[1-(7-aminopro ylJ-ii,5-dimethhydantoinl-B-met ne.igogropylhydantoinyaq-nyihydantoinyl-al n odecane.

11 one. G. oi amine curing agent per 4.35 5.45 6.26.

g. oi epoxide resin 0. Curing conditions 24 hours at 40 0. plus 6 hoursat 100 C. Tensile shear strength on 2.44 kgJn'lm. r 1 1 1 V 1.17 kgJmm.1.50 hgJmmJ. Curring conditions v 24 hours at 40 plus B at 100 C.Tensile shear strength on 1.44 kg./mt:1. 1.17 kgJmm. 1.50 kgJmmJ;

"Anticorodal B Assessment of the cured Scratch-resistant, somewhatbrittle Scratch-resistant, somewhat brittle Scratch-resistant coatingwhich after coating coating. No longer becomes tacky coating Is easilyswollen by the repeated bending of the sheet metal after treatment withan aeetoneacetone wiping test. substrate neither tears nor flakes ofl.soaked cottonwool pad. No longer becomes tacky after treatment with anacetone-soaked eottonwool pad,

We claim. toinyl-3'1-n-hexane. l. A di-primary diamine containing twohydantoin 4. l,l2-Bis-[l'-(-y-aminopropyl)-5',5'-dimethylhyrings. offormula dantoinyl-3']-n-dodecane.

R A g h (I) wherein R is straight or branched chain alkylene 0f 25 5.B,/3-Bis-[1-(3'-aminopropyl)-5,S-dimethylhydanfrom 4 to 18 carbon atomswhich may be interrupted toinyl-31-diethyl ether. by a hetero etheratom, wherein R R,', R, and R, each is alkyl of l to 4 carbon atoms, orwherein R and R, or R and R together are methylene or pena stamethylene.

2. 1,4-Bis-(1''-( gamma-aminopropyl)-5''-isopropylhydantoinyl-3'')-n-butane.
 3. 1,6-Bis-(1''-(gamma -aminopropyl)-5'',5''-dimethylhydantoinyl-3'')-n-hexane. 4.1,12-Bis-(1''-( gamma-aminopropyl)-5'',5''-dimethylhydantoinyl-3'')-n-dodecane.
 5. Beta ,Beta ''-Bis-(1-(3''-aminopropyl)-5,5-dimethylhydantoinyl-3)-diethylether.